Process of preparing a nitro-nitroso dimer from an olefinic hydrocarbon and a mixuteof no and no2



United States Patent 3,379,710 PROCESS OF PREPARING A NITRO-NITRQSODIMER FROM AN OLEFHNIC HYDROCAR- BON AND A MIXTURE OF NO AND N0 Alan F.Ellis, Murrysville, Pa., assignor to Gulf Research & DevelopmentCompany, Pittsburgh, Pa., a corporation of Delaware No Drawing.Continuation-in-part of application Ser. No. 517,790, Dec. 30, 1965.This application Nov. 29, 1966, Ser. No. 597,512

14 Claims. (Cl. 260-143) ABSTRACT OF THE DISCLOSURE A process is definedfor the product of a nitro-nitroso dimer by the reaction of a monoolefinor a non-conjugated diolefin with a mixture of NO and N0 wherein themolar ratio of NO to N0 is at least 1:1. The temperature and pressure ofreaction are such that the N0 is substantially entirely in the vaporphase and the stoichiometric ratio of the mixture of NO and N0 to theolefin is less than 0.5.

This invention relates to the preparation of nitro-nitroso dimers by thereaction of selected olefinic hydrocarbons with a nitrosating agent.

This application is a continuation-in-part of my prior co-pendingapplication, Ser. No. 517,790, filed Dec. 30, 1965, now abandoned, andassigned to the same assignee as the present application.

It has been found that certain olefinic hydrocarbons will react with agaseous mixture of NO and N0 to result in the preparation ofnitro-nitroso addition compounds. The nitro-nitroso addition compoundsform solid dimers under the proper conditions. The nitro-nitroso dimerscan be converted thermally, preferably in the presence of aceticanhydride, to nitroolefins which can be converted by hydrogenation inthe normal manner to useful alkyl amines. Due to the usefulness of thesenitro-nitroso dimers, it is desirable to obtain these dimers in as higha yield as possible from the reaction of selected olefins with anitrosating agent consisting of a mixture of NO and N0 wherein the molarratio of NO to N0 is at least 1:1. It has now been found that thenitro-nitroso dimers can be made in high yields by careful control ofreaction conditions and by limiting the stoichiometric ratio of thenitrosating agent to the olefinic hydrocarbon in the reaction zone.

In accordance with the invention, high yields of nitronitroso dimers areproduced by a process which comprises reacting a charge stock comprisingan olefinic hydrocarbon selected from the group consisting of amonoolefinic hydrocarbon and a non-conjugated diolefinic hydrocarbonwith a nitrosating agent consisting of a mixture of NO and N0 whereinthe molar ratio of NO to N0 is at least 1:1 under conditions oftemperature and pressure such that the N0 is substantially entirely inthe vapor phase and wherein the stoichiometric ratio of the nitrosatingagent to the olefinic hydrocarbon is less than 0.5.

The charge stock for this reaction comprises any olefinic hydrocarbonselected from the group consisting of a monoolefinic hydrocarbon and anon-conjugated diolefinic hydrocarbon. The charge stock suitably cancontain between 2 and 25 carbon atoms when the olefinic hydrocarbon is amonoolefin. When the olefinic hydrocarbon is a non-conjugated diolefin,the charge stock can suitably contain between 5 and 25 carbon atoms.Mixtures of monoolefins and non-conjugated diolefins can also beemployed. By a conjugated diolefinic hydrocarbon is meant any diolefinichydrocarbon where the olefinic double bonds are in an alpha-gammarelationship, for example, 1,3-

3,379,710 Patented Apr. 23, 1968 butadiene. Conversely, a non-conjugateddiolefin is an olefinic hydrocarbon containing two olefinic double bondswhich are not in an alpha-gamma relationship to each other.

The preferred olefins are the monoolefins and the more preferred olefinsare the aliphatic and alicyclic monoolefins which have no branching onthe alpha or beta carbon atoms. The preferred olefinic hydrocarbons arethealpha olefins having the formula:

where R can be hydrogen or any aliphatic hydrocarbon. The olefinichydrocarbon charge stock can suitably have between 2 and 25 carbon atomsper molecule, and preferably has between 4 and 16 carbon atoms permolecule. The charge stock can be a single olefin or a mixture ofolefins, such as is obtained by the cracking of wax or by thetelomerization of ethylene. The charge stock can also suitably containdiluent materials which either do not react with the nitrosating agentor which react so much more slowly than the olefinic hydrocarbon thatfor all practical purposes they can be considered inert. Suitablediluent materials include, for example, parafiins, aromatics andnaphthenes. It is preferred that highly polar organic materials beavoided as diluents, since the highly polar organic diluent materialstend to dissolve the desired nitro-nitroso dimers.

Examples of suitable olefinic hydrocarbon charge stocks include but arenot limited to: ethylene; propylene; lbutene; Z-butene; isobutylene;l-pentene; 2-pentene; 1,4- pentadiene; l-hexene; Z-hexene;1,5-hexadiene; cyclohexene; 4-methyl-l-pentene; l-heptene;3-ethyl-1-pentene; loctene; 1,7-octadiene; 3-octene; styrene;- l-decene;3,7- dimethyl-l-octene; l-undecene; l-dodecene; 1,11-dodecadiene;2-cyclohexyl-1-hexene; l-tetradecene; l-hexadecene; l-eicosene; andl-tetracosene.

The nitrosating agent which is useful in the preparation of thenitro-nitroso dimers of this invention consists of a gaseous mixture ofNO and N0 wherein the molar ratio of NO to NO; is at least 1:1. Pure NOis not suitable in this reaction, butNO with small amounts of N0 willserve to prepare the dimers of this invention, since NO in the presenceof N0 and the nitro-nitroso monomer will generate additional N0 radicalsfor use in the reaction. Pure N0 is unsuitable for use in this reaction,and the use of mixtures of NO and N0 wherein the molar ratio of N0 to NOis greater than 1:1 is undesirable since unwanted by-products includingdinitro and nitrated olefins will result. Likewise, the use of N 0 isnot suitable as a nitrosating agent in the process of this invention.Nitrogen trioxide (N 0 is suitable for use in the p ocess of thisinvention as it dissociates into a 1:1 molar mixture of NO and N0 It hasbeen found that in order to obtain high yields of the desirednitro-nitroso dimers, the stoichiometric ratio of the nitrosating agentto the olefinic hydrocarbon must be maintained below 0.5, preferablybelow 0.35. The most preferred stoichiometric ratio is between 0.1 and0.35. As the stoichiometric ratio of the nitrosating agent to olefingoes above 0.5, the yield of the desired dimer falls off drastically.While it is not certain, it is believed that, as the stoichiometricratio of nitrosating agent to olefin increases, some by-products formwhich are highly polar, and above a stoichiometric ratio of 0.5 there isenough by-product to effect solubilization of the dimer which then tendsto form the monomer which, in turn, tends to decompose and form moreundesired by-products. This effect spirals quickly and the yield ofdimer decreases rapidly and suddenly.

The nitro-nitroso monomers which are formed by the process of thisinvention have the nitro (-NO and nitroso (--N:O) groups on adjacentcarbon atoms. These monomers dimerize through the nitroso group. Thenitro-nitroso monomers form colored greenish liquids while the dimersare white crystalline solids. It has been found that when analpha-olefin is employed as the charge stock, and the beta carbon atomhas at least one hydrogen atom, the nitro-nitroso monomers are alwaysthe 1-nitro-2-nitroso, whereas with internal olefins, the distributionof nitro and nitroso groups is random. It has been found that when thediolefins, such as 1,5-hexadiene, are employed as the charge stock, theN adds unexpectedly to primarily only one of the olefinic bonds to thesubstantial exclusion of the other.

It is also important to maintain conditions of temperature and pressurein the reaction zone such that the N0 is substantially entirely in thevapor phase and also to maintain conditions of temperature and pressurein the reaction zone so that the nitro-nitroso dimer at least partiallyprecipitates during reaction. In general, the reaction can be carriedout at a temperature between about 0 and the melting point of the dimer,which in most cases is between about 55 and 100 C. Temperatures below 0C. are not preferred since it becomes more difficult to maintain the N0in the gaseous phase. Temperatures between and 60 C. are preferred withthe most preferred temperatures being between and 50 C. The highertemperatures favor solution of the dimer in the solvent and dissociationof dissolved dimer into monomer which, in turn, decomposes to unwantedside products. The melting point of the dimer represents the upper limitof reaction temperature since if it is not possible for the dimer to atleast partially precipitate during reaction, it tends to decompose morerapidly into other undesirable nitrated products. It is preferred thatmost of the dimer precipitate during reaction because when the dimer isdissolved in the reaction medium, it tends to form the nitro-nitrosomonomer which is very unstable and it in turn tends to form unwantedby-products, such as dinitro compounds, nitronitrites, nitroolefins,etc. The precipitated dimer does, however, present slurry problems andcare must be taken to have a sufficient amount of solvent in the form ofexcess olefin, paraffin, aromatic, etc. present to allow the slurry tobe pumped.

The reaction pressure will depend somewhat on the exact nature of thenitrosating agent employed. If N 0 is employed, the pressure ispreferably atmoshperic so that in reality a gaseous mixture of NO and N0in a 1:1 molar ratio is added. Even low pressures will tend to liquefythe N0 to form N 0 which will add to the olefinic hydrocarbon chargestock to form unwanted dinitro compounds, nitro-nitrites, etc. ratherthan the desired nitro-nitroso dimers. On the other hand, if NO withonly small amounts of N0 is used, increased reaction pressures aid inthe formation of the desired dimers since an increased pressure aids inthe formation of N0 from the NO in the presence of the nitro-nitrosomonomers. As the amount of N0 increases in the mixture of NO and N0which is used as the nitrosating agent to a maximum of about 1:1 molarratio, then the maximum pressure which can be tolerated decreases inorder to avoid any substantial liquefication of the N0 with thesubsequent undesired formation of by-products. The optimum temperatureand pressure conditions will therefore vary depending on the exactnitrosating agent but should be such that the N0 is maintainedsubstantially entirely in the vapor phase. As a general range, thereaction pressure can vary between 0.5 and 20 atmospheres with preferredpressures depending on the nitrosating agent as noted above.

The addition of the nitrosating agent to the olefinic hydrocarbon is anexothermic reaction and care must be taken during the addition to avoidlocal over-heating since increased temperatures promote the solution ofthe dimer and consequent formation of unwanted byproducts. The local hotspots or overheating ca be avoided by rapid mixing together with propersparging of the nitrosating agent into the olefinic hydrocarbon. It is,of course, critical that the nitrosating agent be added, preferably inthe gaseous state, to the olefinic hydrocarbon to better controltemperature and to avoid the high stoichiometric ratios of nitrosatingagent to olefin.

The reaction time depends upon the olefin conversion desired and thecooling efficiency of the reactor and is merely the time required to addthe necessary amount of nitrosating agent at a rate that allows goodtemperature control. In general, the reaction time is between 0.5 and 10hours or more, with the usual reaction time being between 1 and 3 hours.

The desired solid nitro-nitroso dimer can be separated from the reactionmixture by any suitable procedure. Suitable procedures includefiltration and centrifugation. Distillation of the reaction mixture toremove the unreacted olefins, and diluents is not desirable unlessoperated under very low pressures in order to avoid heating the dimer totemperatures about 50 C.

The invention will be further illustrated with reference to thefollowing experimental work.

In most of the experimental work, octene-l was the olefinic hydrocarbonemployed. In some runs, as noted, the octene-l was admixed with hexane,benzene or heptane. The charge stock was added to a one-liter stirredstainless steel autoclave and the nitrosating agent was sparged throughthe charge stock at pressures between 0 and p.s.i.g. Unless otherwiseindicated, the temperature was maintained at 40 C. by internal coolingcoils and by regulating the rate of addition of the nitrosating agent.The total reaction time varied between i and 3 hours.

After reaction, the solid dimer was separated by filtration. Analysis ofthe solid was by melting point, elemental analysis and infrared. In mostruns, octene-l was the olefin employed and elemental analysis showed thedimer to have the empirical formula C l-1 N 0 On melting, the dimerformed a green liquid which is characteristic of the nitro-nitrosomonomer. The melting point was about 94.5" C. The infrared band spectrawere the same as those published by I. F. Brown, Jr., in J.A.C.S., vol.77, p. 6341, 1955, for an octene-l nitro-nitroso dimer. The liquidfiltrate on further cooling and standing yielded a second crop ofcrystal solids which analyzed the same as the first crop of solids.

Example 1 In the run for this example, the charge stock consisted offour moles of octene-l. Liquid N 0 was vaporized to a 1:1 molar mixtureof NO and N0 and this gaseous mixture was used as the nitrosating agent.The nitrosating agent was passed through a sparger and hubbled throughthe octene-1 held at 36 C. for a period of one hour at which time 0.66mole of N 0 had been added. The stoichiometric ratio of effectivenitrogen oxides to olefin was 0.66:4 or 0.165. That is, N 0 is a 1:1molar ratio of NO to N0 and since the nitro-nitroso monomer contains 1mole of olefm per mole of NO and N0 the stoichiometric ratio of N 0 toolefin is the same as the mole ratio or" N 0 to olefin. The weight ofdimer isolated was 89 grams. The mole percent conversion based on the N0 added was 16.5% (the N 0 was completely consumed). The efiiciency ofthe reaction to the formation of dimer based on the N 0 consumed is 72%,i.e. 0.66 mole of N 0 reacted with 0.66 mole of octene-l and shouldyield an expected 0.66 mole of nitronitroso monomer or 124 grams; butonly 89 grams were recovered so the efliciency is 89 divided by 124 or72%.

Example 2 Example 1 was repeated except 0.69 mole of N 0 were added, thereaction pressure was 5070 p.s.i.g. and the reaction temperature was 33C. The weight of dimer recovered was only 46 grams which reduced theefiiciency of the reaction to 35%.

A comparison of Examples 1 and 2 shows the important effect of pressurewhen a nitrosating agent containing a large amount of N is employed.Under the pressure conditions of Example 2, a considerable amount of theN0 would be in the liquid phase in the form of N 0 This undoubtedlypromoted the formation of dinitro and other unwanted by-products whichdrastically reduced the efficiency of the reaction to the formation ofthe desired dimer.

Example 3 In the run for this example, the charge stock was a mixture of2 moles of octene-l and enough hexane so that the volume percentoctene-l in the mixture was 38%. The nitrosating agent was gaseous NOcontaining a small amount (about 0.02%) of N0 The reaction pressure was100 p.s.i.g. while the reaction temperature was 40 C. The nitrosatingagent was added at the rate of 1.5 moles/hr. until 3.5 moles of NO hadbeen added. The Weight of dimer isolated was 86 grams. The percentconversion based on the amount of nitrosating agent added and assumingits complete conversion was 35%. The efi'iciency of the reaction to theformation of dimer was 66%, again based on the amount of nitrosatingagent added. The actual weight increase in the product was 43 grams andthe percent conversion and efiiciency based on the weight increase inproduct was 30% and 77%, respectively.

The stoichiometric ratio of effective nitrogen oxides to olefin inExample 3 is not the same as the mole ratio of NO to olefin since NOmust be used to prepare N0 in accordance with the following equations:

Adding Equations 1 through 5.results in Equation 6 below.

(6) RCH=CH +4NO- RCHCH NO +N +NO then RCHOHzNOz+ r'ro n nonmog andadding 6 and 7 gives Equation 8 RCH=CH2 N0 RtlHCHzNOz N2 N 2 Hence, a1:1 stoichiometric ratio of etfective nitrogen oxides to olefin whenusing NO catalyzed with N0 is the same as a 5:1 mole ratio of NO toolefin if it is assumed the catalytic amount of N0 added initially isnegligible. It can be noted from the above that effective nitrogenoxides means a 1:1 molar ratio of NO to N0 Based on the above, thestoichiometric ratio of etfective nitrogenoxides to olefin in Example 3was 3.5/5 moles effective nitrogen oxides divided by 2 moles of olefinor 0.35. ince it is assumed all of the effective nitrosating agent isconsumed, the percent conversion based on the eifective nitrosa-tingagent is 35% as noted above.

Example 4 Example 3 was repeated except benzene was used in place ofhexane. The weight increase in the product was 46 grams and the weightof recovered dimer was 79 grams. The conversion and efiiciency based onthe nitrosating agent were 35 and 60%, respectively, while theconversion and efiiciency based on the weight increase in product were30% and 70%, respectively.

Example 5 Example 3 was repeated except 5 moles of olefin were employedand no hexane was added. The olefin was effectively being used as thesolvent. The weight increase in the product was 49 grams and weight ofrecovered dimer was 78 grams. The percent conversion based on thenitrosating agent consumed and the weight increase was 14% and 13%,respectively. The efiiciency to the formation of dimer based on thenitrosating agent and the weight increase was 59% and 64%, respectively.The stoichiometric ratio of eifective nitrogen oxides to olefin was0.14.

A comparison of Examples 1 and 3 shows that N 0 and NO catalyzed with N0are both eflective nitrosating agents.

A comparison of Examples 3, 4 and 5 shows the advantage of using asolvent such as hexane or benzene rather than excess olefin. It isbelieved these solvents render the reaction system more non-polar whichresults in a slightly higher efficiency reaction.

Example 6 Example 3 was repeated except the total moles of NO added wasincreased to 4.5 for a stoichiometric ratio of 0.45. The weight increasein product was 67 grams and the weight of dimer recovered was 106 grams.The percent conversion based on the nitrosating agent added and weightincrease was 45 and 44, respectively, and the corresponding efiiciencieswere 63 and 64.

Example 7 Example 3 was repeated except the stoichiometric ratio ofeffective nitrogen oxides was increased to 0.60 by using only one moleof octene-l in hexane (19% by volume olefin) and adding 3 moles of NOcatalyzed with N0 The weight increase in product was 61 grams but theweight of recovered dimer was only 27 grams. The conversion based againon the nitrosating agent added and Weight increase was 60 and 81%,respectively. The efiiciency to dimer formation based on nitrosatingagent added and weight increase was 12 and 9 percent, respectively.

A comparison of Examples 1, 3, 4, 5, 6 and 7 shows the criticality ofmaintaining the stoichiometric ratio of nitrosating agent to olefinbelow 0.5. At ratios below 0.5 (Examples 1, 3, 4 and 5) the efiiciencyto the formation of the desired dimer is high. At a stoichiometric ratioof 0.6 (Example 7) the efiiciency drops drastically to about 10.

Example 8 Example 3 was repeated except heptane was used as the solvent,the rate of addition of NO was reduced to 1.2 moles/hour and thereaction temperature was increased to 80 C. The weight increase was 36grams and 60 grams of dimer were isolated. The percent conversion basedon the nitrosating agent and weight increase was 35 and 24,respectively, and the corresponding efficiencies were 50% and 67%,respectively.

A comparison of Examples 3 and 8 shows that an increased temperature ofreaction results in a decreased efiiciency of reaction to the dimer.

Example 9 Example 3 was repeated except hexene-l was used as theolefinic hydrocarbon and a total of four moles of NO were added at arate of 1.05 moles per hour. The stoichiometric ratio of nitrosatingagent to hexene-l was 0.45. A white crystalline solid precipitatedduring reaction and this solid formed a greenish liquid on melting.

Example Example 3 was repeated except dodecene-l (1.7 moles) wasemployed as the olefinic hydrocarbon in a volume percent mixture withhexane. The recovery of solid dimer was 123 grams. The conversion andeliiciency based on the nitrosating agent added were 41% and 66%,respectivcly.

Example 11 Example 3 was repeated except hexadecene-l (1.3 moles) wasemployed as the olefinic hydrocarbon in a 47 volume percent mixture withhexane. The recovery of solid dimer was 146 grams. The conversion andefficiency based on the nitrosating agent were 43 and 91%, respectively.

Eicosene-l was also run in a manner similar to Example 3 above and awhite solid crystalline product was recovered.

Example 12 In the run for this example, 2 moles of octene-2 are admixedwith 2 moles of hexane and NO containing a small amount of N0 is bubbledthrough at the rate Of 1.5 moles per hour until 3.5 moles of NO areadded. A white crystalline nitro-nitroso dimer precipitates during thereaction which is held at C. and 100 p.s.i.g.

Example 13 In the run for this example, 41 grams (0.5 mole) of1,5-hexadiene were dissolved in 800 milliliters of nhexane. A total of12 grams (0.16 mole) of gaseous N 0 was added over a period of one hour.A side stream of NO was also continuously added at the rate of 0.219cubic feet per hour. The side stream of NO was added to insure at leasta 1:1 molar ratio of NO to N0 The reaction temperature was maintained atabout 25 29 C. for a reaction time of one hour, during which time awhite precipitate was formed. The precipitate was filtered, washed, andhad a melting point of 74-75 C. Nuclear magnetic resonance showed thestructure to be the dimer of 6-nitro-5-nitroso-1-hexene.

Example 14 In the run for this example, grams (0.73 mole) of1,4-pentadiene were dissolved in 400' milliliters of nhexane. A total of17 grams (0.22 mole) of gaseous N 0 was added over a period of 1.5hours. A total of 0.157 cubic feet of NO was added over the 1.5-hourreaction period to insure at least a 1:1 molar ratio of NO to N0 A whiteprecipitate formed as in Example 13 indicating a dimer had formed. Thereaction conditions included a temperature of 0 C. and a pressure ofatmospheric.

Example 15 In the run for this example, 54 grams (one mole) of1,3-butadiene were dissolved in 500 milliliters of carbon tetrachloride.A total of 23 grams (0.30 mole) of gaseous N 0 was added over a reactiontime of 2.25 hours at atmospheric pressure. A side stream of NO wasadded at the rate of 0.015 cubic feet per hour. The temperature wasmaintained at 6 C, to 0 C. during the run. During the reaction, a redviscous oil immiscible in the reaction medium was observed to form andfloat on top of the carbon tetrachloride. The red oil was separated andcooled to Dry Ice temperatures where it formed a red amorphous solidrather than the white crystalline form characteristic of thenitro-nitroso dimers of this invention.

A comparison of Examples 13-15 shows that nonconjugated diolefins, suchas 1,5-hexadiene and 1,4-pentadiene form the nitro-nitroso dimers ofthis invention, whereas, conjugated diolefins, such as 1,3-butadicne,form an oily type product instead of the solid dimers of this invention.

8 Example 16 In the run for this example, 168 grams (2 moles) ofcyclohexene were dissolved in 400 milliliters of n-hexane. A total of 38grams (0.5 mole) of N 0 were added over a period of two hours. A totalof 0.26 cubic feet of NO was added over the same twohour time period toinsure at least a 1:1 molar ratio of NO to N0 The reaction conditionsincluded a temperature between 5 and 10 C. and a pressure ofatmospheric. A white crystalline product precipitated indicating anitro-nitroso dimer was formed. The dimer was found to have a meltingpoint of 152 C.

Example 16 shows that cyclic monoolefins are also useful to form thenitro-nitroso dimers of this invention,

In all of the above examples, the conditions of reaction were such thatthe N0 was substantially entirely in the gaseous phase, and a Whitecrystalline nitro-nitroso dimer precipitated during the reaction exceptin Example 14 where the conjugated diolefin was employed.

Resort may be had to such variations and modifications as fall withinthe spirit of the invention and the scope of the appended claims.

I claim:

1. A process for the production of a nitro-nitroso dimer which comprisesreacting a charge stock comprising an olefinic hydrocarbon selected fromthe group consisting of a monoolefin and a non-conjugated diolefin witha nitrosating agent comprising a mixture of NO and N0 wherein the molarratio of NO to N0 is at least 1:1 under conditions of temperature andpressure such that the N0 is substantially entirely in the vapor phaseand wherein the stoichiometric ratio of the nitrosating agent to theolefinic hydrocarbon is less than 0.5.

2. A process according to claim 1 wherein the conditions are such thatsaid nitro-nitroso dimer at least partially precipitates duringreaction.

3. A process according to claim 1 wherein the olefinic hydrocarbon hasthe formula:

where R is selected from the group consisting of hydrogen and analiphatic hydrocarbon having between 1 and 23 carbon atoms.

4. A process according to claim 3 wherein the nitrosating agent isselected from the group consisting of N 0 and NO catalyzed with N0 5. Aprocess according to claim 4 wherein the stoichiometric ratio of thenitrosating agent to the olefinic hydrocarbon is between 0.1 and 0.35.

6. A process according to claim 5 wherein the temperature is maintainedbetween 0 C. and the melting point of the dimer.

7. A process according to claim 5 wherein the temperature is maintainedbetween 20 and 50 C.

8. A process according to claim 6 wherein the olefinic hydrocarbon isoctene-l.

9. A process according to claim 6 wherein the charge stock comprises anolefinic hydrocarbon and a solvent selected from the group consisting ofparafiins and aromatics.

10. A process according to claim 9 wherein the olefinic hydrocarbon isoctene-l and the parafiinic solvent is hexane.

11. A process according to claim 1 wherein the olefinic hydrocarbon is anon-conjugated diolefin.

12. A process according to claim 11 wherein the diolefin is1,5-hexadiene.

13. A process according to claim 11 wherein the diolefin isl,4-pentadiene.

14. A process according to claim 1 wherein the olefinic hydrocarbon iscyclohexene.

(References on following page) References Cited UNITED OTHER REFERENCESEmmons, J. Am. Chem. 50 0., vol. 79, pp. 6522 to 6524 (1957).

STATES PATENTS Blackley 260--467 Tanaka et a1. 260143 r L W Y RUTLEDGE EDoumani et a1. 260647 X mmmer Motz at al- 2 0 647 CARL D. QUARFORTH,Exammer.

Flanagan 260-647 L. A, SEBASTIAN, Assistant Examiner.

